Amorphous modification of 1,1&#39;,1&#34;-nitrilo(triethyl-tris-[2,2&#39;-methylene-bis(4,6-di-tert-butylphenyl)] phosphite)

ABSTRACT

The new amorphous modification of 1,1&#39;,1&#34;-nitrilo{triethyl-tris-[2,2&#39;-methylene-bis(4,6-di-tert-butylphenyl)]phosphite} is obtained by cooling rapidly said compound from the melt to ambient temperature. This amorphous form is an effective process stabilizer for polyolefins, particularly polypropylene.

This invention pertains to a novel amorphous modification of1,1',1"-nitrilo-{triethyl-tris-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)]phosphite},to a process for preparing said modification, and to compositionsstabilized therewith.

BACKGROUND OF THE INVENTION

1,1',1"-Nitrilo{triethyl-tris-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)]phosphite}is a compound having the formula I ##STR1##

This compound of formula I is useful as a processing stabilizer fororganic polymers as taught in U.S. Pat. Nos. 4,318,845 and 4,374,219.The compound of formula I is disclosed as being a white powder meltingat 175°-181° C. The relatively high melting point of the "white powder"form of the compound of formula I as disclosed in the above mentionedpatents is a problem when stabilizing organic polymers processed atrelatively low temperatures such as blow molding of HDPE and processingof natural rubber. As a result, the additive is not uniformlydistributed within the organic polymer causing problems in thestabilization performance of the additive stabilizer.

In accordance with the present invention an amorphous form of thecompound of formula I is obtained which does not suffer the problemsassociated with the higher melting powder reported previously. This newamorphous form is characterized by a glass transition temperature(T_(g)) within the range of 120°-124° C. as determined by differentialscanning calorimetry (DSC). Additionally the amorphous form of thepresent invention gave a featureless X-ray diffraction pattern obtainedusing Cu--K.sub.α.

Additionally, the new amorphous form of the compound of formula I ismore soluble in organic solvents such a lubricating oils, lubricants andin urethanes, prepolymers and the like. The instant amorphous form notonly dissolves more rapidly, but also forms compatible solutions in ashort time. This is of enormous practical advantage in many end-useapplications.

The instant invention also relates to a process for the preparation ofthis novel amorphous modification of the compound of formula I.

The instant invention also pertains to a composition stabilized againstthermal, oxidative and actinic induced degradation which comprises

(a) an organic material subject to thermal, oxidative or actinic induceddegradation, and

(b) an effective stabilizing amount of the amorphous form of1,1',1"-nitrilo{triethyl-tris-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)]phosphite}, characterized by a glass transition temperature (T_(g)) of120°-124° C. as determined by differential scanning calorimetry (DSC);and by an X-ray diffraction pattern which is featureless.

The organic material is preferably a polymer processed at elevatedtemperatures. Particularly preferred organic polymers are thepolyolefins, especially polypropylene and polyethylene, and polyamides.Most particularly the organic polymer is polypropylene.

The compound of this invention is a very effective processingstabilizers for polyolefins than the prior art compounds both inpreventing molecular weight changes as well as preventing discoloration.

In general polymers which can be stabilized include

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), low densitypolyethylene (LDPE), linear low density polyethylene (LLDPE), branchedlow density polyethylene (BLDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

(a) radical polymerisation (normally under high pressure and at elevatedtemperature).

(b) catalytic polymerisation using a catalyst that normally contains oneor more than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerisationmedium. The catalysts can be used by themselves in the polymerisation orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/DPE) and mixtures of different types of polyethylene(for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅ -C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer; and blockcopolymers of styrene such asstyrene/butadiene/styrene,/isoprene/styrene,/ethylene/butylene/styreneor styrene/ethylene/propylene/styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, copolymers ofethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers,especially polymers of halogen-containing vinyl compounds, for examplepolyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride,polyvinylidene fluoride, as well as copolymers thereof such as vinylchloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidenechloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer, polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from polyepoxides, for example frombisglycidyl ethers or from cycloaliphatic diepoxides.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO.

29. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

31. Polysiloxanes such as the soft, hydrophilic polysiloxanes described,for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

32. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

33. Radiation curable compositions containing ethylenically unsaturatedmonomers or oligomers and a polyunsaturated aliphatic oligomer.

34. Epoxymelamine resins such as light-stable epoxy resins crosslinkedby an epoxy functional coetherified high solids melamine resin such asLSE-4103 (Monsanto).

In general, the compounds of the present invention are employed in fromabout 0.01 to about 5% by weight of the stabilized composition, althoughthis will vary with the particular substrate and application. Anadvantageous range is from about 0.05 to about 3%, and especially 0.05to about 1%.

The stabilizer of the instant invention may readily be incorporated intothe organic polymers by conventional techniques, at any convenient stageprior to the manufacture of shaped articles therefrom. For example, thestabilizer may be mixed with the polymer in dry powder form, or asuspension or emulsion of the stabilizer may be mixed with a solution,suspension, or emulsion of the polymer. The resulting stabilized polymercompositions of the invention may optionally also contain from about0.01 to about 5%, preferably from about 0.025 to about 2%, andespecially from about 0.1 to about 1% by weight of various conventionaladditives, such as the materials listed below, or mixtures thereof.

1. Antioxidants

1.1. Alkylated monophenols, for example,

2,6-di-tert-butyl-4-methylphenol

2-tert-butyl-4,6-dimethylphenol

2,6-di-tert-butyl-4-ethylphenol

2,6-di-tert-butyl-4-n-butylphenol

2,6-di-tert-butyl-4-i-butylphenol

2,6-di-cyclopentyl-4-methylphenol

-2(α-methylcyclohexyl)-4,6-dimethylphenol

2,6-di-octadecyl-4-methylphenol

2,4,6-tri-cyclohexylphenol

2,6-di-tert-butyl-4-methoxymethylphenol

1.2. Alkylated hydroquinones, for example,

2,6-di-tert-butyl-4-methoxyphenol

2,5-di-tert-butyl-hydroquinone

2,5 -di-tert-amyl-hydroquinone

2,6-diphenyl-4-octadecyloxyphenol

1.3. Hydroxylated thiodiphenyl ethers, for example,

2,2'-thio-bis-(6-tert-butyl-4-methylphenol)

2,2'-thio-bis-(4-octylphenol)

4,4'-thio-bis-(6-tert-butyl-3-methylphenol)

4,4'-thio-bis-(6-tert-butyl-2-methylphenol)

1.4. Alkylidene-bisphenols, for example,

2,2'-methylene-bis-(6-tert-butyl-4-methylphenol)

2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol)

2,2'-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]

2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol)

2,2'-methylene-bis-(6-nonyl-4-methylphenol)

2,2'-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-(4,6-di-tert-butylphenol)

2,2'-ethylidene-bis-(4,6-di-tert-butylphenol)

2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)

4,4'-methylene-bis-(2,6-di-tert-butylphenol)

4,4'-methylene-bis-(6-tert-butyl-2-methylphenol)

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol

1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane

ethyleneglycol bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate]

di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

di-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

1.5. Benzyl compounds, for example,

1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide

3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester

bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate

1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate

1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,calcium-salt

1.6. Acylaminophenols, for example,

4-hydroxy-lauric acid anilide

4-hydroxy-stearic acid anilide

2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine

octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate

1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxphenyl)-propionic acid withmonohydric or polyhydric alcohols, for example,

    ______________________________________                                        methanol       diethylene glycol                                              octadecanol    triethylene glycol                                             1,6-hexanediol pentaerythritol                                                neopentyl glycol                                                                             tris-hydroxyethyl isocyanurate                                 thiodiethylene glycol                                                                        di-hydroxyethyl oxalic acid diamide                            ______________________________________                                    

1.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acidwith monohydric or polyhydric alcohols, for example,

    ______________________________________                                        methanol       diethylene glycol                                              octadecanol    triethylene glycol                                             1,6-hexanediol pentaerythritol                                                neopentyl glycol                                                                             tris-hydroxyethyl isocyanurate                                 thiodiethylene glycol                                                                        di-hydroxyethyl oxalic acid diamide                            ______________________________________                                    

1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid forexample,

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

N,N '-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

1.10 Diarylamines, for example,

diphenylamine, N-phenyl-1-naphthylamine,N-(4-tert-octylphenyl)-1-naphthylamine,

4,4'-di-tert-octyl-diphenylamine, reaction product ofN-phenylbenzylamine and

2,4,4-trimethylpentene, reaction product of diphenylamine and2,4,4-trimethylpentene,

reaction product of N-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.

2. UV absorbers and light stabilizers

2.1. 2-(2'-Hydroxyphenyl)-benzotriazoles, for example, the

5'-methyl-,3',5'-di-tert-butyl-,

5'-tert-butyl-,5'-(1,1,3,3-tetramethylbutyl)-,5-chloro-3',5'-di-tert-butyl-

5-chloro-3'-tert-butyl-5'-methyl-,3'-sec-butyl-5'-tert-butyl-,4'-octoxy,3',5'-di-tert-amyl-, 3',5'-bis-(α,α-dimethylbenzyl),

3 '-tert-butyl-5'-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,

3'-dodecyl-5'-methyl-, and 3'-tert-butyl-5'-(2-octyloxycarbonyl)ethyl-,and

dodecylated-5'-methyl derivatives.

2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-,4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy-and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of optionally substituted benzoic acids for example, phenylsalicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate,dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

2.4. Acrylates, for example, α-cyano-β,β-diphenylacrylic acid ethylester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester,α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester,α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

2.5.Nickel compounds, for example, nickel complexes of2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl) sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

2.7. Oxalic acid diamides, for example, 4,4'-di-octyloxy-oxanilide,2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide,2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide,2-ethoxy-2'-ethyl-oxanilide, N,N'-bis (3-dimethylaminopmpyl)-oxalamide,2-ethoxy-5-tert-butyl-2-ethyloxanilide and its mixture with2-ethoxy-2-ethyl-5,4-di-tert-butyloxanilide and mixture of ortho-andpara-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.

3. Metal deactivators, for example, N,N'-diphenyloxalic acid diamide,N-salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine,N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, di-isodecylpentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl) 4,4'-diphenylylenediphosphonite.

5. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydrogenated tallow mine.

8. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example Castearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate,antimony pyrocatecholate or zinc pyrocatecholate.

10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipicacid, diphenylacetic acid.

11. Fillers and reinforcing, for example, calcium carbonate, silicates,glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxidesand hydroxides, carbon black, graphite.

12. Other additives, for example, plasticizers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, anti-static agents,blowing agents and thiosynergists such as dilauryl thiodipropionate ordistearyl thiodipropionate.

13. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312,3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The co-stabilizers, with the exception of the benzofuranones listedunder 11, are added for example in concentrations of 0.01 to 10%,relative to the total weight of the material to be stabilize.

Further preferred compositions comprise, in addition to components (a)and (b) further additives, in particular phenolic antioxidants, lightstabilizers or processing stabilizers.

Particularly preferred additives are phenolic antioxidants (item 1 ofthe list), sterically hindered amines (item 2.6 of the list), phosphitesand phosphonites (item 4 of the list) and peroxide-destroying compounds(item 5.) of the list.

Additional additives (stabilizers) which are also particularly preferredare benzofuran-2-ones, such as described, for example, in U.S. Pat. No.4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312.

Examples of such benzofuran-2-ones are compounds of the formula ##STR2##in which

R₁₁ is phenyl or phenyl which is substituted by 1 to 3 alkyl radicalstogether having at most 18 carbon atoms, alkoxy having 1 to 12 carbonatoms, alkoxycarbonyl having 2 to 18 carbon atoms or chlorine;

R₁₂ is hydrogen;

R₁₄ is hydrogen, alkyl having 1 to 12 carbon atoms, cyclopentyl,cyclohexyl or chlorine;

R₁₃ has the meaning of R₁₂ or R₁₄ is a radical of the formula ##STR3##in which

R₁₆ is hydrogen, alkyl having 1 to 18 carbon atoms, alkyl having 2 to 18carbon atoms which is interrupted by oxygen or sulfur, dialkylaminoalkylhaving a total of 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenylor phenyl which is substituted by 1 to 3 alkyl radicals together havingat most 18 carbon atoms;

n is 0, 1 or 2;

the substituents R₁, independently of one another, are hydrogen, alkylhaving 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenylwhich is substituted by 1 or 2 alkyl radicals together having at most 16carbon atoms, a radical of the formula --C₂ H₄ OH, --C₂ H₄ --O--C_(m)H_(2m+1) or ##STR4## together with the nitrogen atom to which they areattached form a piperidine or morpholine radical;

m is 1 to 18;

R₂₀ is hydrogen, alkyl having 1 to 22 carbon atoms or cycloalkyl having5 to 12 carbon atoms;

A is alkylene having 2 to 22 carbon atoms which may be interrupted bynitrogen, oxygen or sulfur;

R₁₈ is hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl,cyclohexyl, phenyl, phenyl which is substituted by 1 or 2 alkyl radicalstogether having at most 16 carbon atoms, or is benzyl;

R₁₉ is alkyl having 1 to 18 carbon atoms;

D is --O--, --S--, --SO--, --SO₂ -- or --C(R₂₁)₂ --;

the substituents R₂₁, independently of one another, are hydrogen, C₁-C₁₆ alkyl, the two R₂₁ together containing 1 to 16 carbon atoms, R₂₁ isfurthermore phenyl or a radical of the formula ##STR5## in which n, R₁₆and R₁₇ are as defined above;

E is a radical of the formula ##STR6## in which R₁₁, R₁₂ and R₁₄ are asdefined above; and

R₁₅ is hydrogen, alkyl having 1 to 20 carbon atoms, cyclopentyl,cyclohexyl, chlorine or a radical of the formula ##STR7## in which R₁₆and R₁₇ are as defined above, or R₁₅ together with R₁₄ forms atetramethylene radical.

Preference is given to those benzofuran-2-ones in which R₁₃ is hydrogen,alkyl having 1 to 12 carbon atoms, cyclopentyl, cyclohexyl, chlorine ora radical of the formula ##STR8## or --D--E, in which n, R₁₆, R₁₇, D andE are as defined above, R₁₆ is in particular hydrogen, alkyl having 1 to18 carbon atoms, cyclopentyl or cyclohexyl.

Preference is given furthermore to those benzofuran-2-ones in which R₁₁s phenyl or phenyl which is substituted by 1 or 2 alkyl radicalstogether having at most 12 carbon atoms; R₁₂ is hydrogen; R₁₄ ishydrogen or alkyl having 1 to 12 carbon atoms; R₁₃ is hydrogen, alkylhaving 1 to 12 carbon atoms, ##STR9## or --D--E; R₁₅ is hydrogen, alkylhaving 1 to 20 carbon atoms, ##STR10## R₁₅ together with R₁₄ forms atetramethylene radical, n, R₁₆, R₁₇, D and E being as defined at thebeginning.

Of particular interest are also those benzofuran-2-ones in which R₁₁ isphenyl; R₁₃ is hydrogen, alkyl having 1 to 12 carbon atoms or --D--E;R₁₂ and R₁₄, independently of one another, are hydrogen or alkyl having1 to 4 carbon atoms; and R₁₅ is alkyl having 1 to 20 carbon atoms, D andE being as defined at the beginning.

Of special interest are finally also those benzofuran-2-ones in whichR₁₁ is phenyl; R₁₃ is alkyl having 1 to 4 carbon atoms or --D--E; R₁₂and R₁₄ are hydrogen; and R₁₅ is alkyl having 1 to 4 carbon atoms,cyclopentyl or cyclohexyl, D being a group --C(R₂₁)₂ -- and E being aradical of the formula ##STR11## the substituents R₂₁ being identical toor different from one another and each being alkyl having 1 to 4 carbonatoms, and R₁₁, R₁₂, R₁₄ R₁₅ being as defined.

The amount of additional additives, in particular stabilizers, forexample of the benzofuran-2-ones mentioned, can vary within wide limits.For example, 0.0005 to 10, preferably 0.001 to 5, in particular 0.01 to2, % by weight thereof can be present in the compositions according tothe invention.

Incorporation of the amorphous form of1,1',1"-nitrilo{triethyl-tris-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)]phosphite} and, if desired, further additives in the polymer organicmaterial is carried out by known methods, for example before or duringmoulding or by applying the dissolved or dispersed compounds to thepolymer organic material, if appropriate with subsequent slowevaporation of the solvent. The amorphous modification according to theinvention can also be added to the materials to be stabilized in theform of a masterbatch containing them, for example, in a concentrationof 2.5 to 25% by weight

The amorphous modification according to the invention can also be addedbefore or during polymerization or before crosslinking.

The amorphous modification according to the invention can beincorporated in the material to be stabilized in pure form orencapsulated in waxes, oils or polymers.

The amorphous modification according to the invention can also besprayed onto the polymer to be stabilized. They are capable of dilutingother additives (for example the abovementioned customary additives) ortheir melts, thus enabling them to be sprayed onto the polymer to bestabilized also together with these additives. Addition by sprayingduring deactivation of the polymerization catalysts is particularlyadvantageous, it being possible, for example, for the steam used fordeactivation to be used for spraying.

In the case of bead polymerized polyolefins, it may be advantageous, forexample, to apply the amorphous modification according to the invention,if desired together with other additives, by spraying.

The materials thus stabilized can be used in a wide range of forms, forexample as films, fibres, tapes, moulding compositions, profiles or asbinders for paints, adhesives or cements.

As already mentioned, the organic materials to be protected arepreferably organic, in particular synthetic, polymers. Of these, thematerials being protected are particularly advantageously thermoplasticmaterials, in particular polyolefins. The excellent efficiency of theamorphous form of1,1',1"-nitrilo{triethyl-tris-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)]phosphite}as a processing stabilizer (thermal stabilizer) should be mentioned inparticular. To this end, it is advantageously added to the polymerbefore or during its processing. It is however also possible tostabilize other polymers (for example elastomers) or lubricants orhydraulic fluids against degradation, for example light-induced orthermal-oxidative degradation. For elastomers, see the above list ofpossible organic materials.

Suitable lubricants and hydraulic fluids are based, for example, onmineral or synthetic oils or mixtures thereof. Lubricants are known toone skilled in the art and described in the relevant technicalliterature, for example in Dieter Klamann, "Schmierstoffe und verwandteProdukte" (Verlag Chemic, Weinheim 1982), in Schewe-Kobek, "DasSchmiermittel-Taschenbuch" (Dr. Alfred Huthig-Verlag, Heidelberg, 1974)and in "Ullmanns Enzyklopadie der technischen Chemie" vol. 13, pages85-94 (Verlag Chemie, Weinheim, 1977).

Accordingly, a preferred embodiment of the present invention is theprocess of using the amorphous form of1,1',1"-nitrilo{triethyl-tris-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)]phosphite}for stabilizing organic materials against oxidative, thermal orlight-induced degradation.

The amorphous modification according to the invention is preferably usedas processing stabilizer (thermal stabilizer) of thermoplastic polymers.

The present invention also provides a process for stabilizing an organicmaterial against oxidative, thermal or light-induced degradation, whichcomprises incorporating therein or applying thereto the amorphous formof1,1',1"-nitrilo{triethyl-tris-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)]phosphite}.

The phenolic antioxidant of particular interest is selected from thegroup consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate ), di-n-octadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,3,6-dioxaoctaraethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol,2,2'-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate,1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris-[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, and N,N'-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

A most preferred phenolic antioxidant is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2'-ethylidene-bis-(4,6-di-tert-butylphenol).

The hindered amine compound of particular interest is selected from thegroup consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane,polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazineand 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4'-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, polycondensation product of2,4-dichloro-6-morpholino-s-triazine and4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N',N",N"'-tetrakis[(4,6-bis-(butyl-2,2,6,6-tetramethyl-piperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,mixed[2,2,6,6-tetramethylpiperidin-4-yl/β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, mixed[1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]undecane)diethyl]1,2,3,4-butanetetracarboxylate,octamethylene bis(2,2,6,6-tetramethylpiperidin-4-carboxylate),4,4'-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one), andbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperdine andsuccinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N',N",N"'-tetrakis[(4,6-bis(butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecaneor bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

The lubricating oil may be a mineral oil, a synthetic oil or any mixtureof such oils. Mineral oils are preferred and examples of these includeparaffinic hydrocarbon oils e.g. a mineral oil having a viscosity of 46mm² /s at 40° C.; "150 Solvent Neutral" a solvent refined neutralmineral oil having a viscosity of 32 mm² /s at 40° C.; and "solventbright-stocks", a high boiling residue from the process of refiningmineral oil, and having a viscosity of 46 mm² /s at 40° C.

Synthetic lubricating oils which may be present may be synthetichydrocarbons such as polybutenes, alkyl benzenes and poly-alpha olefinsas well as simple di-, tri- and tetra-esters, complex esters andpolyesters derived from carboxylic acid esters of formula: G₁-OCC-alkylene-COOG₂ wherein "alkylene" denotes an alkylene residuehaving from 2 to 14 carbon atoms and G₁ G₂ are the same or different andeach is an alkyl group having from 6 to 18 carbon atoms. Tri-esterswhich are of use as lubricating oil base stocks are those derived fromtrimethylolpropane and C₆ -C₁₈ mono-carboxylic acids or mixturesthereof, whereas suitable tetra-esters include those derived frompentaerythritol and a C₆ -C₁₈ mono-carboxylic acid or mixtures thereof.

Complex esters suitable for use as components of the composition of thepresent invention are those derived from monobasic acids, dibasic acidsand polyhydric alcohols, for instance the complex ester derived fromtrimethylol propane, caprylic acid and sebacic acid.

Suitable polyesters are those derived from any aliphatic dicarboxylicacid having from 4 to 14 carbon atoms and at least one aliphaticdihydric alcohol having from 3 to 12 carbon atoms, e.g. those derivedfrom azelaic acid or sebacic acid and 2,2,4-trimethylhexane-1,6-diol.

Other lubricating oils are those known to the art-skilled and describede.g. in Schewe-Kobek, "Schmiermittel-Taschenbuch", (Huethig Verlag,Heidelberg 1974), and in D. Klamarm, "Schmierstoff und verwandteProdukte", (Verlag Chemic, Weinheim 1982).

The lubricating oils applicational media can also contain otheradditives which may be added to improve the basic properties oflubricants e.g. metal passivators, viscosity-index improvers, pour-pointdepressants, dispersing agents, detergents, additional rust inhibitors,extreme pressure additives, anti-wear additives and antioxidants.

Examples of phenolic antioxidants

1. Alkylated Monophenols

2,6-Di-tert-butyl-4-methylphenol,2,6-di-tert-butylphenol,2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethyl-phenol,2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-i-butylphenol,2,6-di-cyclopentyl-4-methylphenol,2-(β-methylcyclohexyl)-4,6-dimethylphenol,2,6-di-octa-decyl-4-methylphenol,2,4,6-tri-cyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, o-tert-butylphenol.

2. Alkylated Hydroquinones

2,6-Di-tert-butyl-4-methoxyphenol,2,5-di-tert-butyl-hydroquinone,2,5-di-tert-amyl-hydroquinone,2,6-diphenyl-4-octa-decyloxyphenol.

3. Hydroxylated Thiodiphenylethers2,2'-Thio-bis-(6-tert-butyl-4-methylphenol),2,2'-thio-bis-(4-octyl-phenyl),4,4'-thio-bis-(6-tert-butyl-3-methylphenol),4,4'-thio-bis-(6-tert-butyl-2-methylphenol).

4. Alkylidene-Bisphenols

2,2'-Methylene-bis-(6-tert-butyl-4-methylphenol),2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol),2,2'-methylene-bis-(4-methyl-6-(α-methyl-cyclohexyl)-phenol),2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol),2,2'-methylene-bis-(6-nonyl-4-methylphenol),2,2'-methylene-bis-(4,6-di-tert-butylphenol),2,2'-ethylidene-bis-(4,6-di-tert-butylphenol),2,2'-ethylidene-bis-(6-tert-butyl-4- or-5-isobutylphenol),2,2'-methylene-bis-(6-(α-methylbenzyl-4-nonylphenol),2,2-methylene-bis-(6-(α,α-di-methylbenzyl)-4-nonylphenol),4,4'-methylene-bis-(2,6-di-tert-butyl-phenol),4,4'-methylene-bis-(6-tert-butyl-2-methylphenol),1,1-bis-(5-tert-butyl-4-hydroxy-2-methyl-phenol)-butane,2,6-di-(3-tert-butyl-5-methyl-2-hydroxy-benzyl)-4-methylphenol,1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecyl)-mercaptobutane,ethyleneglycol-bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate],bis-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene,bis-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-,4-methyl-phenyl]-terephthalate.

5. Benzyl Compounds

1,3,5-Tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethyl-benzene,bis(3,5-di-tert-butyl-4-hydroxybenzyl)-sulfide,3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic acid-isooctylester,bis-(4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl)dithiolterephthalate,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate,1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate,3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid-dioctadecylester,3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid-monoethylester,calcium-salt.

6. Acylaminophenols

4-Hydroxy-lauric acid anilide, 4-hydroxy-stearic acid anilide,2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine,N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamic acid octyl ester.

7. Esters of β-(3,5Di-tert-butyl-4-hydroxyphenl)-propionic acid withmono- or polyhydric alcohols, for example with methanol, isooctylalcohol, 2-ethylhexanol, diethylene glycol, octadecanol, triethyleneglycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol,tris-hydroxyethyl isocyanurate, thiodiethylene glycol,bis-hydroxyethyl-oxalic acid diamide.

8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acidwith mono- or polyhydric alcohols, for example with methanol, isooctylalcohol, 2-ethylhexanol, diethylene glycol, octadecanol, triethyleneglycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol,tris-hydroxyethyl isocyanurate,thiodiethylene glycol,di-hydroxyethyl-oxalic acid diamide.

9. Amides of β-(3,5-Di-tert-butyl-4-hydroxyphenyl)-propionic acid forexampleN,N'-Bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine,N,N'-bis-(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-trimethylene-diamine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.

Examples of amine antioxidants:

N,N'-Di-isopropyl-p-phenylenediamine,N,N'-di-sec.-butyl-p-phenylenediamine,N,N'-bis(1,4-dimethyl-pentyl)-p-phenylenediamine,N,N'-bis(1-ethyl-3-methyl-pentyl)-p-phenylenediamine,N,N'-bis(1-methyl-heptyl)-p-phenylenediamine,N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine,N,N'-di-(naphthyl-2-)-p-phenylenediamine,N-isopropyl-N'-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,N-(1-methyl-heptyl)-N'-phenyl-p-phenylenediamine,N-cyclohexyl-N'-phenyl-p-phenylenediamine,4-(p-toluene-sulfonamido)diphenylamine,N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, di-phenylamine,N-allyldiphenylamine, 4-isopropoxy-diphenylamine,N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylateddiphenylamine, e.g. p,p'-di-tert-octyldiphenylamine,4-n-butylaminophenol, 4-butyrylamino-phenol, 4-nonanoylamino-phenol,4-dodecanoylamino-phenol, 4-octadecanoyl-amino-phenol,di-(4-methoxy-phenyl)-amine,2,6-di-tert-butyl-4-dimethyl-amino-methyl-phenol,2,4'-diamino-diphenylmethane, 4,4'-diaminodiphenyl-methane,N,N,N',N'-tetramethyl-4,4'-diamino-diphenylmethane,1,2-di-(phenyl-amino)-ethane, 1,2-di-[2-methyl-phenyl)-amino]-ethane,1,3-di-(phenylamino)-propane, (o-tolyl)-biguanide,di-[4-1',3'-dimethyl-butyl)-phenyl]amine, tert-octylatedN-phenyl-1-naphthylamine, mixture of mono- and dialkylatedtert-butyl-/tert-octyldiphenylamines,2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine,N-allylphenothiazine, tert-octylated phenothiazine,3,7-di-tert-octylphenothiazine.

Examples for other antioxidants:

Aliphatic or aromatic phosphites, esters of thiodipropionic acid or ofthiodiacetic acid, or salts of dithiocarbamic or dithiophosphoric acid.

Examples of metal passivators, for example for copper, are:

Triazoles, benzotriazoles and derivatives thereof, tolutriazole andderivatives thereof, e.g. di(2-ethylhexyl)-aminomethyltolutriazole,2-mercaptobenzothiazole, 5,5'-methylene-bis-benzotriazole,4,5,6,7-tetrahydrobenzo-triazole, salicyclidene-propylene-diamine andsalicyclamino-guanidine and salts thereof, 1,2,4-triazole and N,N'-disubstituted aminomethyl triazoles of formula ##STR12## in which R₈and R₉ are, independently, e.g. alkyl, alkenyl, or hydroxyethyl,obtained by reacting 1,2,4-triazole with formaldehyde and an amine, HNR₈R₉, as disclosed in European Patent Application No. 160620; and theMannich reaction products derived from benzotriazole or tolutriazole,formaldehyde and an amine HNR₈ R₉.

Examples of rust inhibitors are:

a) Organic acids, their esters, metal salts and anhydrides, e.g.N-oleoyl-sarcosine, sorbitan-mono-oleate, lead-naphthenate,alkenyl-succinic acids and -anhydrides, e.g. dodecenyl-succinic acidanhydride, succinic acid partial esters and amines,4-nonyl-phenoxy-acetic acid.

b) Nitrogen-containing compounds, e.g.

I. Primary, secondary or tertiary aliphafic or cycloaliphatic amines andamine-salts of organic and inorganic acids, e.g. oil-solublealkyl-ammonium carboxylates

II. Heterocyclic compounds, e.g. substituted imidazolines andoxazolines.

c) Phosphorus-containing compounds, e.g. amine salts of phosphonic acidor phosphoric acid partial esters, zinc dialkyldithio phosphates.

d) Sulfur-containing compounds, e.g.barium-dinonylnaphthalene-n-sulfonates, calcium petroleum sulfonates.

e) Derivatives of gamma-alkoxypropylamines described in Japanese PatentPublication No. 15783/1973; and

f) Salts having the formula Y--NH₃ --R₁₀ CO₂ -- in which Y is a groupR₁₁ X₁ CH₂ CH(OH) CH₂ in which R₁₀ and R₁₁, independently, are e.g.alkyl and X₁ is O,CO₂,NH,N(alkyl), N(alkenyl) or S, these salts beingprepared by mixing an amine Y-NH₂ with an acid R₁₀ CO₂ H, as disclosedin DE-OS 3437 876 (German Offenlegungsschrift).

g) Compounds having the formula

    R.sub.12 --X.sub.2 --CH.sub.2 --CH(OH)--CH.sub.2 NR.sub.13 R.sub.14

in which X₂ is --O--, --S--, --SO₂ --C(O)--O-- or --N(Rd) in which R₁₂is H or C₁ -C₁₂ alkyl, R₁₃ is unsubstituted C₁ -C₄ alkyl or C₂ -C₅ alkylsubstituted by one to three hydroxyl groups, R₁₄ is hydrogen,unsubstituted C₁ -C₄ alkyl or C₂ -C₅ alkyl substituted by one to threehydroxyl groups provided that at least one, of R₁₃ and R₁₄ ishydroxy-substituted, and R₁₂ is C₂ -C₂₀ alkyl --CH₂ --CH(OH)--CH₂ NR₁₃R₁₄ or R₁₂ is C₂ -C₁₈ alkenyl, C₂ -C₃ alkynyl or C₅ -C₁₂ cycloalkylprovided that, when X₂ is --O-- or --C(O)--O--, R₁₂ is branched C₄ -C₂₀alkyl. These compounds are described in GB Patent Specification2172284A.

h) Compounds having the formula: ##STR13## in which R₁₅, R₁₆, R₁₇ are,independently, hydrogen, C₁ -C₁₅ alkyl, C₅ -C₁₂ cycloalkyl, C₆ -C₁₅ arylor C₇ -C₁₂ aralkyl and R₁₈ R₁₉, independently, are hydrogen,2-hydroxyethyl or 2-hydroxypropyl, provided that R₁₈ and R₁₉ are notsimultaneously hydrogen and, when R₁₈ and R₁₉ are each --CH₂ CH₂ OH, R₁₅and R₁₆ are not Simultaneously hydrogen and R₁₇ is not pentyl. Thesecompounds are described in EP Patent specification 0 252 007.

Examples of viscosity-index improvers are: Polyacrylates,polymethacrylates, vinylpyrrolidone/methacrylate-copolymers,polyvinylpyrrolidones, polybutanes, olefin-copolymers,styrene/-acrylate-copolymers, polyethers.

Examples of pour-point depressants are: Polymethacrylates, alkylatednaphthalene derivatives.

Examples of dispersants/detergents are: Polybutenylsuccinic acid-amidesor-imides, polybutenyl-phosphonic acid derivatives, basic magnesium-,calcium-, and bariumsulfonates and -phenolates.

Examples of anti-wear additives and extreme pressure additives are:Sulphur- and/or phosphorus- and/or halogen-containing compounds e.g.sulphurised vegetable oils, zinc dialkyldithiophosphates,tritolylphosphate, chlorinated paraffins, alkyl- and aryldi- andtrisulphides, triphenylphosphorothionate.

The process for the preparation of the instant amorphous modification ofthe compound of formula I comprises heating a melt of any of the solidforms of the compound of formula I and rapidly cooling the melt. Thepreferred method consists of pouring the molten material onto a coolsurface maintained below 100° C., more preferably near 25° C. Theamorphous solid thus obtained may be further ground or granulated intoany desired particle size by conventional means.

The present invention also provides a process for stabilizing an organicmaterial against oxidative, thermal or light-induced degradation, whichcomprises incorporating therein or applying thereto the new amorphousform of1,1',1"-nitrilo{triethyl-tris-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)]phosphite}.

Differential scanning calorimetry (DSC) measurements are obtained on aTA Instrument Inc., 910 differential scanning calorimeter, with a 100mL/min nitrogen purge, aligned aluminum pan, temperature scan at 5°C./min to 350° C.

X-ray diffraction patterns are recorded on a Philips Norelco X-rayDiffractometer unit, using Cu--K.sub.α radiation with a nickel filter.

EXAMPLE 1

The compound of formula I,1,1',1"-nitrilo{triethyl-tris-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)]phosphite},is prepared according to procedure of Example 3 of U.S. Pat. No.4,318,845. The product obtained is heated at 200° C. until a clear meltis obtained. The melt is cooled rapidly to ambient temperature to yielda glassy solid with a T_(g) (DSC) of 120°-124° C. The white solid isconveniently found into a white powder using a mortar and pestle. TheX-ray diffraction pattern obtained using Cu--K.sub.α for the instantamorphous compound is featureless whereas the prior an compound ofExample 3 of U.S. Pat. No. 4,318,845 shows a crystalline pattern clearlydifferent from the featureless pattern found for the instant amorphouscompound.

EXAMPLE 2 Bulk Density

This example illustrates the superior packaging properties of the novelamorphous solid modification of the compound of formula I as prepared inExample 1 as compared to the powder form of the compound of Example 3 ofU.S. Pat. No. 4,318,845.

The apparent bulk density of the solids is measured according to themethod of ASTM D-1895 (79). A higher apparent bulk density allows for agreater mass per unit volume which affords advantages in packaging ofthe solid product, such as lower costs for the packaging material, lessstorage space is required, etc.

    ______________________________________                                        Compound of      Bulk Density (g/mL)                                          ______________________________________                                        Example 1 (amorphous                                                                           0.43                                                         solid form)                                                                   Example 3 of     0.33                                                         U.S. 4,318,845                                                                (prior art)                                                                   ______________________________________                                    

The instant amorphous solid form prepared in Example 1 has a much higherbulk density than the prior art compound of Example 3 of U.S. Pat. No.4,318,845 with its concomitant superior packaging properties.

EXAMPLE 3 Process Stabilization of Polypropylene at 525° F. (274° C.)

The blank formation comprises unstabilized polypropylene (PROFAX 6501,Himont) containing 0.075% by weight of calcium stearate. The testadditives are incorporated into the polyproyplene by dry blending or,when the additive is a liquid, using a minimum amount of methylenechloride solvent. The solvent is then removed by evaporation underreduced pressure. The stabilized resin formulation is extruded at 90 rpmfrom a 1 inch (2.54 cm) diameter extruder at 525° F. (274° C/) with aresidence time of 90 seconds. After each of the first, third and fifthextrusions, the melt flow rate (in grams/10 minutes) is determined byASTM method D 1238 on the pellets obtained from the extruder.

The instant compound is effective in stabilizing polypropylene againstthermal and oxidative degradation as shown by a minimum change in themelt flow rate in the presence of a representative phenolic antioxidantand is essentially as effective as the prior art compound of U.S. Pat.No. 4,318,845.

Pellets obtained after the first, third and fifth extrusions arecompression molded into 125 mil (3.2 mm) plaques at 450° F. (232° C.)and the yellowness index (YI) values are determined according to ASTMmethod D 1925. Lower YI values indicate less discoloration.

The instant compound is effective in stabilizing polypropylene againstdiscoloration as shown by a minimum change in the yellowness index inthe presence of a representative phenolic antioxidant and is essentiallyas effective as the prior an compound of U.S. Pat. No. 4,318,845.

EXAMPLE 4 Solubility in Lubricating Oil

The following experiments are performed to determine the solubility ofamorphous compound A and prior an compound B in Mobil BB oil. Bothcompounds have the same uniform particle sizes (40-70 micron).

Compounds Tested

Compound A=amorphous form of1,1',1"-nitrilo{triethyl-tris-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)]phosphite},prepared in accordance with instant Example 1.

Compound B=powder form of1,1',1"-nitrilo{triethyl-tris-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)]phosphite},prepared in accordance with Example 3 of U.S. Pat. No. 4,318,845.

Test Procedure and Results

Experiment 4a

Into a vial of 980 mg. of Mobil BB oil is added 20 mg. of compound A atambient temperature. For the first 60 minutes, the vial is shaken every15 minutes. After the initial 60 minutes, the vial is left standing. Allof compound A dissolves into the oil after hours to give a clearsolution.

Experiment 4b

Into a vial of 980 mg. of Mobil BB oil is added 20 mg. of compound B atambient temperature. For the first 60 minutes, the vial is shaken every15 minutes. After the initial 60 minutes, the vial is left standing.After 3 hours, compound B gives a cloudy suspension.

Experiment 4c

Into a vial of 980 mg. of Mobil BB oil is added 20 mg. of compound A atambient temperature. The vial is then placed into a 60° C. oil bath.After 20 minutes, all of compound A dissolves into the oil to give aclear solution.

Experiment 4d

Into a vial of 980 mg. of Mobil BB oil is added 20 mg. of compound B atambient temperature. The vial is then placed into a 60° C. oil bath.After 20 minutes, compound B gives a cloudy suspension.

    ______________________________________                                               % by weight                                                            Exp. # Test Compound                                                                             Temp.   Observation Time                                   ______________________________________                                        4a     2% A        RT      Clear solution                                                                            3 hrs.                                 4b     2% B        RT      Cloudy Suspension                                                                         3 hrs.                                 4c     2% A        60° C.*                                                                        Clear solution                                                                            20 min.                                4d     2% B        60° C.*                                                                        Cloudy suspension                                                                         20 min.                                ______________________________________                                         *The temperature reading is the oil bath temperature.                    

In summary, the instant amorphous Compound A shows a faster rate ofdissolving and better solubility in lubricants as compared to the priorart powder form Compound B, This provides better compatibility and moreuniform distribution of the instant compound with an organic materialduring formulation compared to the prior art compound.

EXAMPLE 5

Solubility in LLDPE Film at Various Temperatures

Experiments are carried out to determine the solubility of the instantcompound into linear low density polyethylene (LLDPE) films at 20° C.,40° C. and 60° C. by diffusion-in of a relatively homogeneous particlesize (<70 microns) of the test sample suspended in silicon oil.

Each sample is carefully ground with a mortar and pestle and theparticle size below 70 microns is separated by sieving with a 200 meshscreen. The powder is then suspended in silicon oil(polydimethylsiloxane, L-45, Union Carbide Chemicals) at a concentrationof approximately 38% (wt/wt). A few drops of this suspension is placedon a 10 mil (0.254 mm) thick, 2"×2" (5.08 cm ×5.08 cm) compressionmolded film and a second film of the same dimension is placed on top.The films are gently pressed together so that the suspension forms athin liquid layer between the polymer films. Excess suspension isremoved and the procedure is repeated till a stack of eight films (sixfilms for evaluation) are prepared. The stack is then placed between two2.5"×2.5" (6.35 cm ×6.35 cm) ceramic tiles and wrapped in aluminum foiland held together with a G-clamp. Each stack is aged at 20° C., 40° C.and 60° C. under a nitrogen atmosphere. At specified intervals, a singlefilm is removed from the stack and the excess suspension is washed fromthe film with hexane. The film is then analyzed by X-ray fluorescencefor total phosphorus content LLDPE containing 0, 1000 ppm and 2000 ppmof the test compound are used as standard controls for this X-rayfluorescence method.

The instant amorphous compound of Example 1 is more soluble in LLDPEthan is the prior an compound of Example 3 of U.S. Pat. No. 4,318,845.

EXAMPLE 6 Stabilization of Unsaturated Elastomer

The instant compound of Example 1 is evaluated in an emulsion of SBR(cold polymerized, 23.5% styrene with a 52 Mooney Viscosity). Theunstabilized SBR (60 g) is added to the mixing chamber of a BrabenderPlasticorder set at 150° C. and 60 rpm. After 30 seconds, 0.5% by weightof the compound of instant Example 1 is added to the chamber. Stabilityof the SBR is determined by the time until onset of crosslinking of therubber as indicated by an increase in the torque curve. The samplestabilized by the instant compound has a longer induction time tillcrossing occurs than does the unstabilized SBR.

EXAMPLE 7 Stabilization of Polyol

A premix of 10 g of water, 0.25 g of triethylenetetramine, 2 g of L-5740(silicone surfactant, Union Carbide) and 20 g of ANTIBLAZE® AB-100(chlorinated aromatic flame retardant, Albright & Wilson) is added to200 g of 3000 molecular weight polyether polyol containing thestabilizer package listed below*. The mixture is stirred for fiveminutes with a high speed Lightning Mixer. Then 0.4 g of stannousoctoate is added and the mixture is stirred for 5 seconds. Finally, 125g of toluene diisocyanate (80% 2,6-isomer;, 20% 2,4-isomer) is added.The mixture is stirred for 7 seconds at high speed mixing and is thenpoured into a 10"×10"×5" (25.4 cm ×25.4 cm ×12.7 cm) cardboard box. Thefoam is allowed to rise completely. After standing 5 minutes, the box isremoved and the sample cured in a microwave over for five minutes at 50%power. The foam is then immediately air over cured at 125° C. for threeminutes. The foams are then cut in half for visual assessment ofdiscoloration or scorch. *Stabilizer package:

Control is 2,6-di-tert-butyl-4-methylphenol (BHT) 2000 ppm; and NAUGARD®445 (diphenylamine antioxidant, Uniroyal) 2000 ppm.

Instant package is the above plus 1000 ppm of the compound of Example 1.

Visual inspection of the two foams shows that the foam containing theinstant stabilizer package with the compound of Example 1 present isless discolored than the foam stabilized with the control stabilizerpackage. The instant compound demonstrates better scorch protection.

EXAMPLE 8 Stabilization of Polycarbonate

Additive free bisphenol A polycarbonate (LEXAN® 141-111N, GeneralElectric) is dried and blended with 0.3 weight percent of abenzotriazole UV absorber (TINUVIN® 329, Ciba-Geigy) and 0.08 weightpercent of instant compound of Example 1. The mixture is extruded andpelletized at 550° F. (288° C.) on a 1" (2.54 cm) single screw extruder.Injection molded plaques (2"×2"×125 mil; 5.08 cm ×5.08 cm ×3.175 mm) areprepared in a BOY 30M injection molder at 560° F. (293° C.) with a moldtemperature of 150° C. The resulting plaques are measured for yellownessindex (YI) using ASTM D 1925-70. The plaques containing the instantcompound of Example 1 have a lower YI values than those containing theUV absorber alone demonstrating the better performance achieve by theconcomitant presence of the instant phosphite.

EXAMPLE 9 Stabilization of Poly(ethylene terephthalate)

Poly(ethylene terephthalate), PET (KODAPAR®7352, Eastman Chemical) istumble blended with 0.5% by weight of the compound of instant Example 1.The polymer is then extruded and pelletized at 500° F. (260° C.) in aMPM 1" (2.54 cm) single screw extruder. The pellets are collected,redried and reextruded 5 times. Pellets are collected from eachextrusion pass and the polymer intrinsic viscosity measured. PETcontaining the instant compound of Example 1 shows a higher retention oforiginal intrinsic viscosity through the five extrusion passes than doesPET containing no stabilizer.

EXAMPLE 10 Stabilization of Poly(butylene terephthalate)

Poly(butylene terephthalate), PBT (RYNITE® 9160, DuPont) is tumbleblended with 0.3% by weight of the compound of instant Example 1. Thepolymer is then extruded and pelletized at 260° C. A portion of thecollected pellets are reextruded under the same conditions for a secondpass. The remainder from the first extrusion is injection molded into2"×2"×125 mil (5.08 cm ×5.08 cm ×3.175 mm) plaques at 540° F. (282° C.)with a 100° C. mold temperature in a BOY 30M molder. Intrinsicviscosities of the second pass extrudate and the injection moldedplaques are determined. The PBT containing the instant compound ofExample 1 shows a better retention of intrinsic viscosity value thandoes PBT containing no stabilizer.

The plaques are measured for yellowness index (color) using ASTM D1925-70. The plaques containing the instant compound of Example 1 have alower YI values (less discoloration) than do the plaques prepared fromthe control unstabilized PBT.

EXAMPLE 11 Stabilization of 6,6-Nylon

6,6-Nylon (ZYTEL® 101, DuPont) is thoroughly dried in a vacuum oven andtumble blended with 0.5% by weight of the compound of instant Example 1.The polyamide is extruded on a 1" (2.54 cm) MPM extruder at 575° F.(302° C.). The collected pellets are injection molder at 575° F. (302°C.) with the mold at 150° C. in a BOY 30M injection molder. The plaquesobtained are measured for yellowness index (YI) values using ASTM D1925-70. The plaques containing the instant compound of Example 1exhibit lower YI values (less discoloration) than do the unstabilizedcontrol plaques.

EXAMPLE 12 Stabilization of ABS

A solution of 0.25 g of the instant compound of Example 1 in 40 ml ofhexane/methanol is added to a rapidly stirred suspension of 100 g of ABS(acrylonitrile/butadiene/styrene terpolymer) in 600 g of water. Thesuspension is filtered and dried under vacuum at 40° C. for 40 hours. Tothe dried powder is added 2% by weight of titanium dioxide and 1% byweight of N,N'-ethylenebisstearamide on a two roll mill at 180° C. overfour minutes. Compression molded plaques (0.8 ram) are prepared at 175°C. and placed in an air oven at 180° C. for 45 minutes. The color ofsaid plaques are determined as yellowness index values using ASTM D1925-70. The plaques containing the instant compound of Example 1exhibit lower yellowness index values (less discoloration) than do thecontrol plaques from unstabilized ABS resin.

What is claimed is:
 1. The compound1,1',1"-nitrilo{triethyl-tris-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)]phosphite}having the formula I ##STR14## characterized by a glass transitiontemperature (T_(g)) within the range of 120°-124° C. (DSC) and by anX-ray diffraction pattern which is featureless.
 2. A process for thepreparation of the amorphous form of the compound1,1',1"-nitrilo{triethyl-tris-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)]phosphite}having the formula I ##STR15## characterized by a glass transitiontemperature (T_(g)) within the range of 120°-124° C. (DSC) and by anX-ray diffraction pattern which is featureless, which comprisesmeltingsaid compound and rapidly cooling the melt.
 3. A process according toclaim 2 which comprisespouring the molten material onto a cool surfacemaintained below 100° C.
 4. A process according to claim 3 wherein thecool surface is near 25° C.
 5. A composition stabilized against thermal,oxidative and actinic induced degradation which comprises(a) an organicmaterial subject to thermal, oxidative and actinic induced degradation,and (b) an effective stabilizing mount of the amorphous form of1,1',1"-nitrilo{triethyl-tris-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)]phosphite}having the formula I ##STR16## characterized by a glass transitiontemperature (T_(g)) within the range of 120°-124° C. (DSC) and by anX-ray diffraction pattern which is featureless.
 6. A compositionaccording to claim 5 wherein the organic material is a natural,semi-synthetic or synthetic polymer.
 7. A composition according to claim6 wherein the polymer is a thermoplastic polymer.
 8. A compositionaccording to claim 7 wherein the polymer is a polyolefin.
 9. Acomposition according to claim 8 wherein the polyolefin is polyethyleneor polypropylene.
 10. A composition according to claim 9 wherein thepolyolefin is polypropylene.
 11. A composition according to claim 5which additionally contains a phenolic antioxidant, a light stabilizeror a processing stabilizer.
 12. A composition according to claim 5 whichadditionally contains as a coadditive at least one compound of thebenzofuran-2-one type.
 13. A process for stabilizing an organic materialagainst oxidative, thermal or actinic-induced degradation, whichcomprisesincorporating therein or applying thereto the amorphous form of1,1',1"-nitrilo{triethyl-tris-[2,2'-methylene-bis(4,6-di-tert-butylphenyl)]phosphite}having the formula I according to claim
 1. 14. A composition accordingto claim 5 wherein component (a) is a lubricant, lubricating oil,natural fat or wax, or fat or wax based on a synthetic ester.